Photographic element

ABSTRACT

A photographic element comprising a support having provided thereon a light-sensitive layer and a transparent magnetic recording layer, the magnetic recording layer comprising a transparent polymeric binder, ferro-magnetic particles and abrasive particles, the magnetic particles having a surface area greater than 30 m 2  /gm and a coverage of from about 1×10 -11  mg/μm 3  to about 1×10 -10  mg/μm 3 , the abrasive particles having a median diameter of from about 0.2 to about 0.4 μm, specific surface area greater than 5 m 2  /gm, a Mohs hardness of at least 6 and being present in the transparent magnetic layer in an amount of at least about 30% by weight based on the weight of the magnetic particles present.

This is a continuation of U.S. application Ser. No. 08/193,686, filed 08 Feb. 1994, now abandoned, which is a continuation-in-part of U.S. application Ser. No. 08/171,785, filed 22 Dec. 1993, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to photographic elements and more particularly to photographic elements having a light-sensitive silver halide layer and a transparent magnetic recording layer.

2. Description of Related Art

It is known from various U.S. patents, including: U.S. Pat. Nos. 3,782,947; 4,279,945; 4,990,276; 5,217,804; 5,147,768; 5,229,259, and others; to include in a light-sensitive silver halide photographic element a transparent magnetic recording layer. Such elements are advantageous because they can be employed to record images by the customary photographic process while at the same time information can be recorded into and read from the magnetic recording layer by the techniques similar to that employed in the magnetic recording art.

A difficulty, however, arises in that magnetic recording layers generally employed in the magnetic recording industry are opaque, not only because of the nature of the magnetic particles, but also because of the requirements that the recording layer contains other additives which further create problems with regard to the optical characteristics of the layer. Also, the requirements of recording and reading of the magnetic signal from a transparent magnetic layer present on a photographic element are more stringent than that found in conventional magnetic recording because of the loading of the magnetic particles in the transparent magnetic layer and the nature of the photographic element.

Thus, the presence of the magnetic recording layer cannot interfere with the primary function of the photographic element which is to achieve realistic reproductions of the original image. In addition, the magnetic recording layer must be capable of accurately recording the information applied thereto and reading out the information on demand. This is particularly difficult because the loading and distribution of the magnetic particles in the transparent layer must be such as to not interfere with the quality of the photographic elements.

Finally, the photographic element and particularly the transparent magnetic recording layer provided thereon must be capable of repeated use in both the recording and reading mode and, therefore, must be durable, abrasion resistant and scratch resistant so as not to adversely affect the quality of the photographic element. For example, during the residence of the film in a camera, entries may be made to the magnetic recording layer for every exposure, and an indeterminate number of read operations are conducted depending on the particular application to which the film is used. This also is true in the processing of the film and in subsequent use of the processed film for additional copies, enlargements and the like. Thus, a reasonable number of passes between the film and magnetic heads to which the film will be required to withstand is at least 60.

It can, therefore, be readily seen that it would be highly desirable to provide photographic elements having a transparent magnetic recording layer exhibiting improved magnetic and photographic performance as well as improved running durability, abrasion resistance and scratch resistance. This goal is extremely difficult to achieve because of the nature and concentration of the magnetic particles required to provide sufficient signal to write and read magnetically stored data, the effect of any noticeable color, haze, or grain associated with the magnetic layer on the photographic layers and the effect of the magnetic layer on the optical density and granularity of the photographic layers. Thus, all of these various characteristics must be considered both independently and cumulatively in order to arrive at a commercially viable photographic element containing a transparent magnetic recording layer that will withstand repeated and numerous passages through the recording and reading zones of a suitable apparatus. Also, because of the curl of the element, primarily due to the photographic layers and core set, the film must be held tightly against the magnetic heads by pressures much higher than those in conventional magnetic recording in order to maintain film plane flatness in the recording and reading zone.

SUMMARY OF THE INVENTION

The invention provides an improved photographic element including a support, having provided thereon a light-sensitive layer and a transparent magnetic recording layer, the magnetic recording layer comprising a transparent polymeric binder, ferro-magnetic particles and abrasive particles, the magnetic particles having a surface area greater than 30 m² /gm and a coverage of from about 1×10⁻¹¹ mg/μm³ to about 1×10⁻¹⁰ mg/μm³, (μm=10⁻⁶ meter) the abrasive particles having a median diameter on a weight basis of from about 0.2 to about 0.4 μm and preferably from about 0.2 to about 0.35 μm, a specific surface area greater than 5 m² /gm and a Mohs hardness of at least 6, the abrasive particles being present in the magnetic layer in an amount at least about 30% and preferably at least about 70% by weight and most preferably at least about 90% based on the weight of the magnetic particles present. Because of the requirement that the magnetic layer be transparent in the photographic sense, it was highly unexpected to find that the addition of further particulate material in the form of the abrasive particles described to the magnetic recording layer could be achieved without interfering with the photographic properties of the element while at the same time achieving substantial increase in head cleaning, running durability, abrasion resistance and scratch resistance of the element. When the quantity of the abrasive particles are less than about 30 percent by weight based on the weight of the magnetic particles in the transparent magnetic layer, the number of surface contacts necessary for satisfactory performance drops off significantly.

DETAILED DESCRIPTION OF THE INVENTION

In the preparation of a photographic element having a transparent magnetic recording layer, the magnetic particles have a surface area greater than 30 m² /gm and preferably greater than 40 m² /gm. The coverage ofthe magnetic particles in the magnetic recording layer varies within the ranges given above depending upon the thickness of the magnetic recording layer. For optimum performance, the magnetic recording layer should be such that normal wear will not result in signal loss after multiple reading and writing operations. However, the layer must not be so thick asto interfere with the photographic properties of the film.

The abrasive particles are present in an amount of at least about 30 percent by weight and preferably at least about 70 percent and most preferably at least about 90% based on the weight of the magnetic particles in order to provide the durability and to prevent the clogging of the magnetic heads. The upper limit of the quantity of abrasive particles is controlled by the effect of such particles on various apparatus the photographic film comes in contact with, such as magnetic heads, film cartridges, cameras, photofinishing devices and the like, as well as the optical characteristics of the photographic element.

In accordance with this invention, the abrasive particles are present in the magnetic recording layer in an amount of from about 1 percent to about20 percent by weight based on the weight of the binder present. Most preferably, the abrasive particles are present in an amount of about 1 to 7 percent based on the weight of the binder.

The magnetic particles are present in the magnetic recording layer in an amount of from about 1 to about 10 percent by weight based upon the weightof the binder and most preferably in an amount of 2 to 7 percent.

It has been determined that when the abrasive particles are present in amounts less than about 30 percent based on the weight of the magnetic particles present, the number of reading and writing operations with constant signal drops off significantly because of clogging of the heads.

In accordance with this invention, the transparent magnetic layer is prepared by initially forming a high solids content magnetic concentrate by mixing the magnetic particles in a suitable grind solvent together withsuitable surfactants and milling in a device such as, for example, a ball mill, a roll mill, a high speed impeller mill, media mill, an attritor or a sand mill. Milling proceeds for a sufficient time to ensure that substantially no agglomerates of the magnetic particles remain. The high solids magnetic concentrate is next diluted with suitable solvents and polymeric stabilizers to maintain the particles in an unagglomerated state(subsequently referred to as the intermediate letdown). Mixing for an additional period of time is continued in order to polish the ingredients.

In a separate container, the binder polymer is dissolved in a suitable solvent. To this solution is added the intermediate letdown in accordance with the procedure set forth above and stirring is continued. A dispersionof the abrasive particles is prepared by milling to break up agglomerates of the abrasive particles and this is added to the mixer containing the binder solution and intermediate letdown. This dispersion may be coated onto a suitable support in its present form or additional and optional ingredients such as, crosslinking agents, catalysts, coating aids, lubricants and the like, may be added before the coating operation.

The coating composition is applied to a suitable support which may contain additional layers for promoting adhesion, by any suitable coating device including slot die hoppers, slide hoppers, gravure coaters, reverse roll coaters and the like.

The magnetic layer can also be overcoated with conventional layers including antistats, protective overcoats, lubricants and the like.

Any suitable support may be employed in the practice of this invention, such as, cellulose derivatives including cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetatepropionate and the like; polyamides; polycarbonates; polyesters, particularly polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene 1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate and polyethylene naphthalate; polystyrene, polypropylene, polyethylene, polymethyl-pentene, polysulfone, polyethersulfone, polyarylates, polyether imides and the like. Particularly preferred supports are polyethylene terephthalate, polyethylene naphthalate and the cellulose esters particularly cellulose triacetate.

Thickness of those supports used in the present invention is from 50 μm to 180 μm, preferably, 85 to 125 microns. In addition, various dyes maybe formulated into the support or the magnetic layer to give neutral density.

Depending upon the nature of the support, suitable transparent tie or undercoat layers may be desired. Particularly with regard to polyester supports, primers are used in order to promote adhesion. Any suitable primers in accordance with those described in the following U.S. patents may be employed: U.S. Pat. Nos. 2,627,088; 3,501,301; 4,689,359; 4,363,872; and 4,098,952. Each of these are incorporated herein by reference in their entirety.

The ferromagnetic pigments comprise ferromagnetic iron oxides, such as γ-Fe₂ O₃, Fe₃ O₄ or γ-Fe₂ O₃ or Fe₃ O₄ with Co, Zn or other metals in solid solution or surface treated, or ferromagnetic chromium dioxides, such as CrO₂ or CrO₂ with metallic elements, for example Li, Na, Sn, Pb, Fe, Co, Ni and Zn, or halogen atoms in solid solution. Ferromagnetic metal pigments with an oxide coating on their surface to improve their chemical stabilityor to improve dispersibility, as is commonly used in conventional magnetic recording, may also be used in accordance with the invention. In addition,magnetic oxides with a thicker layer of lower refractive index oxide or other material having a lower optical scattering cross-section as taught in U.S. Pat. Nos. 5,217,804 and 5,252,444 may also be used. Cobalt surfacetreated iron oxide is the preferred ferromagnetic material for use in accordance with this invention.

Examples of the abrasive particles include nonmagnetic inorganic powders with a Mohs scale hardness of not less than 6. Specific examples are metaloxides such as alpha-alumina, chromium oxide (Cr₂ O₃), alpha-Fe₂ O₃, silicon dioxide, alumino-silicate and titanium dioxide; carbides such as silicon carbide and titanium carbide; nitrides such as, silicon nitride, titanium nitride and diamond in fine powder. Alpha alumina and silicon dioxide are the preferred abrasives in accordance with this invention.

The binders used in the magnetic layer include, for example, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-vinyl alcohol copolymers, vinyl chloride-vinyl acetate-maleic acid polymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-acrylonitrile copolymers, acrylic ester-acrylonitrile copolymers,acrylic ester-vinylidene chloride copolymers, methacrylic ester-vinylidene chloride copolymers, methacrylic ester-styrene copolymers, thermoplastic polyurethane resins, phenoxy resins, polyvinyl fluoride, vinylidene, chloride-acrylonitrile copolymers, butadiene-acrylonitrile copolymers, acrylonitrile-butadiene-acrylic acid copolymers, acrylonitrile-butadiene-methacrylic acid copolymers, polyvinyl butyral, polyvinyl acetal, cellulose derivatives, styrene-butadiene copolymers, polyester resins, phenolic resins, epoxy resins, thermosetting polyurethane resins, urea resins, melamine resins, alkyl resins, urea-formaldehyde resins and the like. Of the above, the cellulose derivatives are the preferred binders for use in accordance with this invention. Cellulose derivatives include cellulose esters such as, for example, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, and the like. The most preferred binder is cellulose diacetate. For crosslinking of the binder with isocyanates, the binder should contain active hydrogen atoms as determined by the Zerewitinoff test, such active hydrogen atoms including --OH, --NH₂ --NHR, where R is an organic radical, and the like, as described in U.S. Pat. No. 3,479,310.

A dispersing agent, sometimes referred to as a wetting agent or a surface active agent, can be present in the dispersion to facilitate dispersion ofthe magnetic particles and/or wetting of the particles with the dispersing medium. This helps to further minimize agglomeration of the magnetic particles. The dispersing agent can be present in the dispersion in an amount up to about 0.02%, preferably 0.001 to 0.01%, by weight. Useful dispersing agents include fatty acid amines, and commercially available wetting agents such as Witco Emcol CC59 which is a quaternary amine available from Witco Chemical Corp. Rhodafac PE 510, Rhodafac RE 610, Rhodafac RE 960, and Rhodafac LO 529 which are phosphoric acid esters available from Rhone-Poulenc. Other constituents of the coating composition including grind solvents, coating aids, and solvents for the binder are included. Suitable grind solvents include, for example, an ester of an acid such as phthalic acid. Preferred esters are dialkylestersof phthalic acid, the alkyl portion of which can contain from 1 to about 12, preferably 4 to 8, carbon atoms. Exemplary useful esters include dimethyl phthalate, diethyl phthalate, dioctyl phthalate, dipropyl phthalate, and dibutyl phthalate as disclosed in U.S. Pat. No. 4,990,276 issued to Bishop et al. and assigned to the same assignee as this application.

Suitable coating aids include nonionic fluorinated alkyl esters such as, FC-430, FC-431 sold by Minnesota Mining and Manufacturing Co., polysiloxanes such as, Dow Corning DC 1248, DC 200, DC 510, DC 190 sold byDow Corning and BYK 310, BYK 320, and BYK 322 sold by BYK Chemie and SF 1079, SF 1023, SF 1054 and SF 1080 sold by General Electric.

Organic solvents are normally used for the preparation of the dispersion. Examples of suitable solvents are ketones, such as acetone, methyl ethyl ketone and cyclohexanone, alcohols, esters, such as ethyl acetate and butyl acetate, cellosolves, ethers, such as tetrahydrofuran aromatic solvents, such as toluene, and chlorinated hydrocarbons as solvents, such as carbon tetrachloride, chloroform, dichloromethane; tetrahydrofuran and the ketoesters of U.S. application Ser. No. 08/173,833 filed Dec. 22, 1993, entitled Coating Compositions For A Transparent Magnetic Recording Layer, by R. M. Wexler and assigned to the same assignee as the immediate application, which are preferred.

Optionally, the binder in the magnetic layer may be crosslinked employing any suitable crosslinking agent such as, for example, organic isocyanates;aziridines, as taught in U.S. Pat. No. 4,225,665; and melamines such as methoxymethylmelamine, and the like as set forth in U.S. Pat. No. 5,198,499 to Anderson et al. issued Mar. 30, 1993 and assigned to the sameassignee as this application.

Any suitable organic polyisocyanate can be used as the crosslinking agent such as, tetramethylene diisocyanate, hexamethylene diisocyanate, diisocyanato dimethylcyclohexane, dicyclohexylmethane diisocyanate, isophorone diisocyanate, dimethylbenzene diisocyanate, methylcyclohexylenediisocyanate, lysine diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polymers of the foregoing, polyisocyanates prepared by reacting an excess of an organic diisocyanate with an active hydrogen containing compounds such as polyols, polyethers and polyesters and the like including ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, trimethylol propane, hexanetriol, glycerine, sorbitol, pentaerythritol, caster oil, ethylenediamine, hexamethylenediamine, ethanolamine, diethanolamine, triethanolamine, water, ammonia, urea and the like, including biuret compounds, allophanate compounds and the like. The preferred polyisocyanates employed as a crosslinking agent is the reaction product of trimethylol propane and 2,4-tolylene diisocyanate soldby Mobay under the trade designation Mondur CB 75.

As noted, photographic elements in accordance with this invention comprise at least one photosensitive layer. Such photosensitive layers can be image-forming layers containing photographic silver halides such as silverchloride, silver bromide, silver bromoiodide, silver chlorobromide and the like. Both negative and reversal silver halide elements are contemplated. For reversal films, the emulsion layers as taught in U.S. Pat. No. 5,236,817, especially Examples 16 and 21, are particularly suitable. Any of the known silver halide emulsion layers, such as those described in Research Disclosure, Vol. 176, December 1978 Item 17643 and Research Disclosure Vol. 225, January 1983 Item 22534, the disclosures of which areincorporated by reference in their entirety, are useful in preparing photographic elements in accordance with this invention. Generally, the photographic element is prepared by coating the support film on the side opposite the magnetic recording layer with one or more layers comprising adispersion of silver halide crystals in an aqueous solution of gelatin and optionally one or more subbing layers, such as, for example, gelatin, etc.The coating process can be carried out on a continuously operating machine wherein a single layer or a plurality of layers are applied to the support. For multicolor elements, layers can be coated simultaneously on the composite support film as described in U.S. Pat. Nos. 2,761,791 and 3,508,947. Additional useful coating and drying procedures are described in Research Disclosure, Vol. 176, December 1978, Item 17643. Suitable photosensitive image forming layers are those which provide color or blackand white images.

As is taught in U.S. Pat. No. 3,782,947 noted above, whether an element is useful for both photographic and magnetic recording depends on both the size distribution and concentration of the magnetic particles and on the relationship between the granularities of the magnetic and photographic coatings. Generally, of course, the coarser the grain of the emulsion in the photographic element that contains the magnetic recording layer, the larger the mean size of the magnetic particles which can be tolerated. A magnetic particle concentration between about 10 and 1000 mg/m² when uniformly distributed across the desired area of the photographic element will be sufficiently photographically transparent provided that the maximum particle size is less than about 1 micron. Particle concentrationsless than about 10 mg/m² tend to be insufficient for magnetic recording purposes and particle concentrations greater than about 1000 mg/m² tend to be too dense for photographic purposes. Particularly useful particle concentrations are in the range of 20-70 mg/m². Concentrations of about 20 mg/m² have been found to be particularly useful in reversal films and concentrations of about 40 mg/m² are particularly useful in negative films.

The photographic elements according to this invention can contain one or more conducting layers such as antistatic layers and/or anti-halation layers such as such as described in Research Disclosure, Vol. 176, December 1978, Item 17643 to prevent undesirable static discharges during manufacture, exposure and processing of the photographic element. Antistatic layers conventionally used in color films have been found to besatisfactory for use herewith. Any of the antistatic agents set forth in U.S. Pat. No. 5,147,768, which is incorporated herein by reference may be employed. Preferred antistats include metal oxides, for example, tin oxide, antimony doped tin oxide and vanadium pentoxide.

The photographic elements according to this invention can be provided with a protective or lubricating layer, such as a wax layer, in or over the transparent magnetic recording layer. Suitable lubricants include siliconeoil, silicones having polar groups, fatty acid-modified silicones, fluorine-containing silicones, fluorine-containing alcohols, fluorine-containing esters, polyolefins, polyglycols alkyl phosphates and alkali metal salts thereof, alkyl sulfates and alkali metal salts thereof,polyphenyl ethers, fluorine-containing alkyl sulfates and alkali metal salts thereof, monobasic fatty acids having 10 to 24 carbon atoms (which may contain unsaturated bonds or may be branched) and metal salts thereof (such as Li, Na, K and Cu), monovalent, divalent, trivalent, tetravalent, pentavalent and hexavalent alcohols having 12 to 22 carbon atoms (which may contain unsaturated bonds or may be branched), alkoxy alcohols having 12 to 22 carbon atoms, mono-, di- and tri-esters of monobasic fatty acids having 10 to 24 carbon atoms (which may contain unsaturated bonds or may be branched) and one of monovalent, divalent, trivalent, tetravalent, pentavalent and hexavalent alcohols having 2 to 12 carbon atoms (which maycontain unsaturated bonds or may be branched), fatty acid esters of monoalkyl ethers of alkylene oxide polymers, fatty acid amides having 8 to22 carbon atoms and aliphatic amines having 8 to 22 carbon atoms.

Specific examples of these compounds (i.e., alcohols, acids or esters) include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, butyl stearate, oleic acid, linolic acid, linolenic acid, elaidic acid, octyl stearate, amyl stearate, isooctyl stearate, octyl myristate, butoxyethyl stearate, anhydrosorbitan monostearate, anhydrosorbitan distearate, anhydrosorbitan tristearate, pentaerythrityl tetrastearate, oleyl alcohol and lauryl alcohol. Carnauba wax is preferred.

The invention will be further illustrated by the following examples in which parts and percentages are given by weight unless otherwise specified.

EXAMPLE 1

A cellulose diacetate/cellulose triacetate binder with magnetic particles and abrasive particles is cast to a dry thickness of about 1.2 microns onto subbed polyethylene terephthalate from a dispersion composition as shown in Table 1. This dispersion is prepared by adding a dispersion of the magnetic particle, stabilized with Rhodafac PE 510 and cellulose triacetate, in methylene chloride and dibutyl phthalate to a cellulose diacetate solution in methylene chloride/acetone/methyl acetoacetate usinga high shear mixer. A dispersion of the abrasive particle in propylene glycol monomethyl ether and a stabilizing agent sold by Zeneca, Inc. (ICI)under the trade designation Solsperse 24000 is then added using a high shear mixer. A coating aid is then added with low shear. Subsequently, thecast magnetic layer is overcoated with 2.5 mg/sq. ft. of carnauba wax.

                  TABLE 1                                                          ______________________________________                                         Dispersion Ingredient                                                                            Function      Percent                                        ______________________________________                                         Cellulose Diacetate                                                                              Binder        2.561                                          Cellulose Triacetate                                                                             Binder/Dis-   0.116                                                            persion Stabilizer                                           Toda CSF-4085V2   Magnetic Particle                                                                            0.116                                          Rhodafac PE510    Surfactant    0.005                                          Dibutyl Phthalate Grind Solvent 0.142                                          Norton E-600 (0.35 μm diameter)                                                               Abrasive Particle                                                                            0.035                                          Zeneca Solsperse 24000                                                                           Dispersing Agent                                                                             0.006                                          3M FC-431         Coating Aid   0.015                                          Methylene chloride                                                                               Solvent       67.816                                         Acetone           Solvent       24.221                                         Methyl acetoacetate                                                                              Solvent       4.847                                          Propylene Glycol Methyl Ether                                                                    Solvent       0.12                                           ______________________________________                                    

EXAMPLE 2

A cellulose diacetate/cellulose triacetate binder with magnetic particles and abrasive particles is cast to a thickness of about 1.2 microns onto subbed polyethylene terephthalate from a dispersion composition as shown in Table 2. The dispersion is prepared as in Example 1.

                  TABLE 2                                                          ______________________________________                                         Dispersion Ingredient                                                                            Function      Percent                                        ______________________________________                                         Cellulose Diacetate                                                                              Binder        2.555                                          Cellulose Triacetate                                                                             Binder/Dis-   0.118                                                            persion Stabilizer                                           Toda CSF-4085V2   Magnetic Particle                                                                            0.118                                          Rhodafac PE510    Surfactant    0.006                                          Dibutyl Phthalate Grind Solvent 0.138                                          Norton E-600      Abrasive Particle                                                                            0.074                                          Zeneca Solsperse 24000                                                                           Dispersing Agent                                                                             0.015                                          3M FC-431         Coating Aid   0.015                                          Methylene chloride                                                                               Solvent       67.664                                         Acetone           Solvent       24.167                                         Methyl acetoacetate                                                                              Solvent       4.836                                          Propylene Glycol Methyl Ether                                                                    Solvent       0.296                                          ______________________________________                                    

EXAMPLE 3

A cellulose diacetate/cellulose triacetate binder with magnetic particles and abrasive particles is cast to a thickness of about 1.2 microns onto subbed polyethylene naphthalate from a dispersion composition as shown in Table 3. The dispersion is prepared as in Example 1 except that the abrasive particle is dispersed in methyl acetoacetate prior to addition tothe final dispersion.

                  TABLE 3                                                          ______________________________________                                         Dispersion Ingredient                                                                          Function     Percent                                           ______________________________________                                         Cellulose Diacetate                                                                            Binder       2.550                                             Cellulose Triacetate                                                                           Binder/Dispersion                                                                           0.116                                                             Stabilizer                                                     Toda CSF-4085V2 Magnetic Particle                                                                           0.116                                             Rhodafac PE510  Surfactant   0.005                                             Dibutyl Phthalate                                                                              Grind Solvent                                                                               0.142                                             Norton E-600    Abrasive Particle                                                                           0.115                                             3M FC-431       Coating Aid  0.015                                             Solsperse 24000 Dispersing Agent                                                                            0.023                                             Methylene chloride                                                                             Solvent      67.517                                            Acetone         Solvent      24.114                                            Methyl acetoacetate                                                                            Solvent      5.287                                             ______________________________________                                    

EXAMPLE 4

A cellulose diacetate/cellulose triacetate binder with magnetic particles and abrasive particles is cast to a thickness of about 1.2 microns onto subbed polyethylene terephthalate from a dispersion composition as shown in Table 4. The dispersion is prepared as in Example 3 except that a polyisocyanate crosslinking agent, Mondur CB75, and tin octoate crosslinking catalyst are added prior to casting the film.

                  TABLE 4                                                          ______________________________________                                         Dispersion Ingredient                                                                       Function           Percent                                        ______________________________________                                         Cellulose Diacetate                                                                         Binder             2.4                                            Cellulose Triacetate                                                                        Binder/Dispersion Stabilizer                                                                      0.125                                          Toda CSF-4085V2                                                                             Magnetic Particle  0.125                                          Rhodafac PE510                                                                              Surfactant         0.006                                          Dibutyl Phthalate                                                                           Grind Solvent      0.247                                          Sumitomo AKP-50                                                                             Abrasive Particle  0.45                                           (0.25 μm diameter)                                                          3M FC-431    Coating Aid        0.015                                          Mobay Mondur CB75                                                                           Crosslinking Agent 0.24                                           Tin Octoate  Crosslinking Catalyst                                                                             0.12                                           Methylene chloride                                                                          Solvent            67.39                                          Acetone      Solvent            24.068                                         Methyl acetoacetate                                                                         Solvent            4.814                                          ______________________________________                                    

COMPARATIVE EXAMPLE C-1

A cellulose diacetate/cellulose triacetate binder with magnetic particles and abrasive particles is cast to a thickness of about 1.2 microns onto subbed polyethylene terephthalate from a dispersion composition as shown in Table 5. The dispersion is prepared as in Example 1 except that the abrasive particle is omitted.

                  TABLE 5                                                          ______________________________________                                         Dispersion Ingredient                                                                       Function           Percent                                        ______________________________________                                         Cellulose Diacetate                                                                         Binder             2.565                                          Cellulose Triacetate                                                                        Binder/Dispersion Stabilizer                                                                      0.118                                          Toda CSF-4085V2                                                                             Magnetic Particle  0.118                                          Rhodafac PE510                                                                              Surfactant         0.006                                          Dibutyl Phthalate                                                                           Grind Solvent      0.138                                          3M FC-431    Coating Aid        0.015                                          Methylene chloride                                                                          Solvent            67.926                                         Acetone      Solvent            24.26                                          Methyl acetoacetate                                                                         Solvent            4.854                                          ______________________________________                                    

EVALUATION METHODS

Abrasion/Scratch Resistance

The resistance to abrasion and scratches of lubricated cast: layers is evaluated with a Taber Abraser. This test consists of a turntable on whicha transparent sample is mounted. Two CS10F wheels at a load of 124 grams are in contact with the rotating sample. The wheels turn in opposite directions creating an abrasion track. The abrasion severity is determinedoptically by measuring the difference in haze (reported as % delta haze) produced by the abraded and unabraded sample using an XL-211 Hazegard System which measures transmitted light on a percentage basis for any light deviating by more than 2.5° from the incident beam. The TaberAbraser is typically insensitive to surface lubrication.

Rotating Drum Friction Test

The running durability of the lubricated cast layers is evaluated using a Steinberg Rotating Drum Friction Tester. The initial (breakaway) friction coefficient and final (running) friction coefficient are measured under 50gram load and drum speed of 30 cm/sec at 23° C. and 50% relative humidity. The running friction is measured after 10 minutes. The Rotating Drum Friction Test is sensitive to surface lubrication.

Head Clogging Test

Head clogging of the lubricated cast layers is evaluated using a Honeywell 7600 reel-to-reel transport operating at a tape speed of 3.75 inches per second and a tape tension of 13 ounces. Output signal characterization is performed using a Tektronix 7854 digitizing oscilloscope. Head clogging isdetermined to have occurred if the peak-to-peak output voltage decreased along the length of tape tested.

High Pressure Head Film Interface

Head clogging and film durability are evaluated using a Kodak photofinisherhead-film interface (HFI) which has head loads of about 70 grams. The test method follows the procedure of anhysteretically recording a squarewave pattern on the photographic element and then driving the element forwards and backwards through the HFI while measuring the average amplitude and pulsewidth. The sample is judged to fail if the signal amplitude decreasesby a statistically significant amount in three successive cycles.

                  TABLE 6                                                          ______________________________________                                                               Rotating                                                           Taber       Drum Friction Head                                       Number    % Delta Haze                                                                               Initial  Running                                                                               Clogging                                 ______________________________________                                         Example 1 4.2         0.17     0.07   no                                       Example 2 2.3         0.18     0.04   no                                       Example 3 4.1         0.25     0.11   no                                       Example 4 1.4         0.17     0.08   no                                       Comparative                                                                              4.0         0.23     0.07   yes                                      Example 1                                                                      ______________________________________                                    

As is apparent from the results in Table 6, Examples 1 through 4, that the requirements of this invention offer excellent resistance to abrasion and scratching, excellent running durability, and improved head clogging performance.

EXAMPLES 5-8 AND COMPARATIVE EXAMPLE C-2

A color photographic recording material for color negative development is prepared by applying the following layers in the given sequence to the opposite side of each of the supports of Examples 1-4 and Comparative Example 1 respectively. The quantities of silver halide are given in grams(g) of silver per m². The quantities of other materials are given in gper m².

Layer 1 {Antihalation Layer} black colloidal silver sol containing 0.236 g of silver, with 2.44 g gelatin.

Layer 2 {First (least) Red-Sensitive Layer} Red sensitized silver iodobromide emulsion [1.3 mol % iodide, average grain diameter 0.55 microns, average thickness 0.08 microns] at 0.49 g, red sensitized silver iodobromide emulsion [4 mol % iodide, average grain diameter 1.0 microns, average thickness 0.09 microns] at 0.48 g, cyan dye-forming image coupler C-1 at 0.56 g, cyan dye-forming masking coupler CM-1 at 0.033 g, BAR compound B-1 at 0.039 g, with gelatin at 1.83 g.

Layer 3 {Second (more) Red-Sensitive Layer} Red sensitive silver iodobromide emulsion [4 mol % iodide, average grain diameter 1.3 microns, average grain thickness 0.12 microns] at 0.72 g, cyan dye-forming image coupler C-1 at 0.23 g, cyan dye-forming masking coupler CM-1 at 0.022 g, DIR compound D-1 at 0.011 g, with gelatin at 1.66 g.

Layer 4 {Third (most) Red-Sensitive Layer} Red sensitized silver iodobromide emulsion [4 mol % iodide, average grain diameter 2.6 microns, average grain thickness 0.13 microns] at 1.11 g, cyan dye-forming image coupler C-1 at 0.13 g, cyan dye-forming masking coupler CM-1 at 0.033 g, DIR compound D-1 at 0.024 g, DIR compound D-2 at 0.050 g, with gelatin at 1.36 g.

Layer 5 {Interlayer} Yellow dye material YD-1 at 0.11 g and 1.33 g of gelatin.

Layer 6 {First (least) Green-Sensitive Layer} Green sensitized silver iodobromide emulsion 1.3 mol % iodide, average grain diameter 0.55 microns, average grain thickness 0.08 microns] at 0.62 g, green sensitizedsilver iodobromide emulsion [4 mol % iodide, average grain diameter 1.0 microns, average grain thickness 0.09 microns] at 0.32 g, magenta dye-forming image coupler M-1 at 0.24 g, magenta dye-forming masking coupler MM-1 at 0.067 g with gelatin at 1.78 g.

Layer 7 {Second (more) Green-Sensitive Layer} Green sensitized silver iodobromide emulsion 4 mol % iodide, average grain diameter 1.25 microns, average grain thickness 0.12 microns] at 1.00 g, magenta dye-forming imagecoupler M-1 at 0.091 g, magenta dye-forming masking coupler MM-1 at 0.067 g, DIR compound D-1 at 0.024 g with gelatin at 1.48 g.

Layer 8 {Third (most) Green-Sensitive Layer} Green sensitized silver iodobromide emulsion [4 mol % iodide, average grain diameter 2.16 microns,average grain thickness 0.12 microns] at 1.00 g, magenta dye-forming image coupler M-1 at 0.0.72 g, magenta dye-forming masking coupler MM-1 at 0.056g, DIR compound D-3 at 0.01 g, DIR compound D-4 at 0.011 g, with gelatin at1.33 g.

Layer 9 {Interlayer} Yellow dye material YD-2 at 0.11 g with 1.33 g gelatin.

Layer 10 {First (less) Blue-Sensitive Layer} Blue sensitized silver iodobromide emulsion [1.3 mol % iodide, average grain diameter 0.55, average grain thickness 0.08 microns] at 0.24 g, blue sensitized silver iodobromide emulsion [6 mol % iodide, average grain diameter 1.0 microns, average grain thickness 0.26 microns] at 0.61 g, yellow dye-forming image coupler Y-1 at 0.29 g, yellow dye forming image coupler Y-2 at 0.72 g, cyan dye-forming image coupler C-1 at 0.017 g, DIR compound D-5 at 0.067 g, BAR compound B-1 at 0.003 g with gelatin at 2.6 g.

Layer 11 {Second (more) Blue-Sensitive Layer} Blue sensitized silver iodobromide emulsion [4 mol % iodide, average grain diameter 3.0 microns, average grain thickness 0.14 microns] at 0.23 g, blue sensitized silver iodobromide emulsion [9 mol % iodide, average grain diameter 1.0 microns] at 0.59 g, yellow dye-forming image coupler Y-1 at 0.090 g, yellow dye-forming image coupler Y-2 at 0.23 g, cyan dye-forming image coupler C-1 0.022 g, DIR compound D-5 at 0.05 g, BAR compound B-1 at 0.006 g with gelatin at 1.97 g.

Layer 12 {Protective Layer} 0.111 g of dye UV-1, 0.111 g of dye UV-2, unsensitized silver bromide Lippman emulsion at 0.222 g, 2.03 g.

This film is hardened at coating with 2% by weight to total gelatin of hardener H-1. Surfactants, coating aids, scavengers, soluble absorber dyesand stabilizers are added to the various layers of this sample as is commonly practiced in the art.

The formulas for the component materials are as follows: ##STR1##

                  TABLE 7                                                          ______________________________________                                         Example                                                                               Abrasive/magnetic                                                                             Number of High Pressure HFI                              Number %              Passes to Failure                                        ______________________________________                                         5       30            66                                                       6       64            95                                                       7      100            190                                                      8      360            >250                                                     C-2     0             24                                                       ______________________________________                                    

As is apparent from the results in Table 7, the photographic element of theinvention offers excellent performance over extensive use through a high pressure head-film interface.

The quantity of the abrasive particles, even at the highest levels, do not interfere significantly with the optical qualities of the photographic element.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

What is claimed is:
 1. A photographic element comprising a support having provided thereon a light-sensitive layer and a transparent magnetic recording layer, the magnetic recording layer comprising a transparent polymeric binder, ferro-magnetic particles and abrasive particles, the abrasive particles being present in the transparent magnetic recording layer in an amount of from about 1 to about 20 percent by weight based on the weight of the binder, the magnetic particles having a surface area greater than 30 m² /gm and a coverage of from about 1×10⁻¹¹ mg/μm³ to about 1×10⁻¹⁰ mg/μm³ and being present in the transparent magnetic recording layer in an amount of from about 1 to about 10 percent by weight based on the weight of the binder, the abrasive particles having a median diameter of from about 0.2 to about 0.4 μm, specific surface area greater than 5 m² /gm, a Mohs hardness of at least 6 and being present in the transparent magnetic layer in an amount of at least about 30% by weight based on the weight of the magnetic particles present.
 2. The photographic element of claim 1 wherein the abrasive particles are present in an amount of at least 70% by weight.
 3. The photographic element of claim 1 wherein the abrasive particles are present in an amount of at least 90 percent by weight.
 4. The photographic element of claim 1 wherein the abrasive particles have a median diameter of from 0.2 to 0.35 μm.
 5. The photographic element of claim 1 wherein the polymeric binder is a cellulose ester, a polyurethane or a vinyl polymer.
 6. The photographic element of claim 5 wherein the polymeric binder is crossed-linked.
 7. The photographic element of claim 6 wherein the polymeric is cross-linked by a melamine, and aziridine or an isocyanate.
 8. The photographic element of claim 6 wherein the polymeric binder is cross-linked with an isocyanate.
 9. The photographic element of claim 1 wherein the polymeric binder contains active hydrogen atoms as determined by the Zerewitinoff test.
 10. The photographic element of claim 5 wherein the polymeric binder is a cellulose ester.
 11. The photographic element of claim 5 wherein the polymeric binder is a polyurethane.
 12. The photographic element of claim 5 wherein the polymeric binder is a vinyl polymer.
 13. The photographic element of claim 10 wherein the cellulose ester is a cellulose acetate.
 14. The photographic element of claim 13 wherein the cellulose acetate is cellulose diacetate.
 15. The photographic element of claim 13 wherein the cellulose acetate is cellulose triacetate.
 16. The photographic element of claim 14 wherein the cellulose diacetate is cross-linked with a polyisocyanate.
 17. The photographic element of claim 1 wherein the abrasive particles are alpha aluminum oxide, silicon dioxide, alumino-silicate, or mixtures thereof.
 18. The photographic element of claim 17 wherein the abrasive particles are alpha aluminum oxide.
 19. The photographic element of claim 17 wherein the abrasive particles are silicon dioxide.
 20. A transparent magnetic recording layer comprising a transparent polymeric binder, ferro-magnetic particles and abrasive particles, the abrasive particles beina present in the transparent magnetic recording laverin an amount of from about 1 to about 20 percent by weight based on the weight of the binder, the magnetic particles having a surface area greater than 30 m² /gm and a coverage of from about 1×10⁻¹¹ mg/μm³ to about 1×10⁻¹⁰ mg/μm³ and being present in the transparent magnetic recording layer in an amount of from about 1 to about 10 percent by weight based on the weight of the binder, the abrasive particles having a median diameter of from about 0.2 to about 0.4 μm, a specific surface area of greater than 5 m² /gm, a Mohs hardness of at least 6 and being present in an amount of at least about 30% by weight based on the weight of the magnetic particles present.
 21. The transparent magnetic recording layer of claim 20 wherein the abrasive particles are present in an amount of at least 70% by weight based on the weight of the magnetic particles.
 22. The transparent magnetic recording layer of claim 20 wherein the abrasive particles have a median diameter of from 0.2 to 0.35 μm.
 23. The transparent magnetic recording layer of claim 20 wherein the polymeric binder is a cellulose ester, a polyurethane or a vinyl polymer.
 24. The transparent magnetic recording layer of claim 23 wherein the polymeric binder is crossed-linked.
 25. The transparent magnetic recording layer of claim 24 wherein the polymeric is cross-linked by a melamine, and aziridine or an isocyanate.
 26. The transparent magnetic recording layer of claim 25 wherein the polymeric binder is cross-linked with an isocyanate.
 27. The transparent magnetic recording layer of claim 20 wherein the polymeric binder contains active hydrogen atoms as determined by the Zerewitinoff test.
 28. The transparent magnetic recording layer of claim 23 wherein the polymeric binder is a cellulose ester.
 29. The transparent magnetic recording layer of claim 23 wherein the polymeric binder is a polyurethane.
 30. The transparent magnetic recording layer of claim 23 wherein the polymeric binder is a vinyl polymer.
 31. The transparent magnetic recording layer of claim 28 wherein the cellulose ester is a cellulose acetate.
 32. The transparent magnetic recording layer of claim 31 wherein the cellulose acetate is cellulose diacetate.
 33. The transparent magnetic recording layer of claim 31 wherein the cellulose acetate is cellulose triacetate.
 34. The transparent magnetic recording layer of claim 32 wherein the cellulose diacetate is cross-linked with a polyisocyanate.
 35. The transparent magnetic recording layer of claim 20 wherein the abrasive particles are alpha aluminum oxide, silicon dioxide, alumino-silicate, or mixtures thereof.
 36. The transparent magnetic recording layer of claim 35 wherein the abrasive particles are alpha aluminum oxide.
 37. The transparent magnetic recording layer of claim 35 wherein the abrasive particles are silicon dioxide. 